TW201625354A - Methods for producing borylated arenes - Google Patents

Abstract

Methods for the borylation of aromatic compounds using cobalt catalysts are provided.

Description

Method for preparing an oxyborated aromatic hydrocarbon Cross-reference to related applications

This application claims the benefit of U.S. Patent Provisional Application Serial No. 62/012,681, the entire disclosure of which is incorporated herein by reference.

Field of invention

This application is generally directed to a method of forming an oxyborated aromatic hydrocarbon, and a method of using the same.

Background of the invention

Aryl boronic acid and aryl boronic acid esters are multifunctional reagents in organic chemistry. In particular, aryl boronic acids and aryl boronic esters can participate in various cross-coupling reactions, such as the Suzuki-type cross-coupling reaction, which can result in carbon-carbon bond formation, as outlined below.

Thus, aryl boronates and arylboronic acids are often key intermediates in the synthesis of highly functional organic compounds, including pharmaceuticals and agrochemicals. Modified arylboronic acid and aryl boronic acid ester preparation method, package The regioselective process for the preparation of substituted arylboronic acids and substituted arylborates provides the possibility of improving the synthesis of important classes of organic compounds, including pharmaceuticals and agrochemicals.

Summary of invention

Metal-catalyzed C-H-activated oxyborylation can be used to prepare aryl boronic acids and aryl boronic esters in a single step from their precursors. Metal catalyzed C-H activated oxyborylation provides a number of advantages over the optional oxyborylation process. For example, metal-catalyzed C-H-activated oxyborylation does not require a low temperature reaction temperature, which is typically required when a classical hydrogen-lithium exchange reaction is used to activate the oxyborylation C-H position. However, metal catalyzed C-H activated oxyborylation typically uses expensive rhodium and ruthenium catalyst systems. Provided herein are methods for C-H activated oxyborylation of aromatic compounds using a cobalt catalyst system. The cobalt catalyst system is significantly less expensive than the expensive rhodium and ruthenium catalyst systems typically used for C-H activated oxyborylation.

A method for preparing an oxyborylated aromatic compound is provided. The method for preparing an oxyborylated aromatic compound may comprise contacting an aromatic matrix with a catalytic cobalt complex and an oxyborylating agent under conditions effective to form the boroborylated aromatic compound .

The aromatic matrix can be any suitable aromatic compound that can undergo C-H activated oxyborylation. For example, the aromatic matrix can be a substituted or unsubstituted aryl compound (eg, substituted or unsubstituted benzene), a substituted or unsubstituted six-membered heteroaromatic compound (eg, For example, substituted or unsubstituted pyridine), or substituted or unsubstituted five-membered heteroaromatic compound (eg, substituted or unsubstituted pyrrole, substituted or unsubstituted) Furan, or substituted or unsubstituted thiophene).

In such processes, the catalytic cobalt complex can be any suitable cobalt (I) or cobalt (II) complex capable of catalyzing C-H activated oxyborylation of an aromatic matrix. In some embodiments, the catalytic cobalt complex is a cobalt (I) complex.

In some embodiments, the catalytic cobalt complex can comprise a cobalt-clamping complex containing a tridentate ligand. For example, the catalytic cobalt complex can be a cobalt chelate complex. In some examples, the catalytic cobalt complex can be a cobalt-clamped complex containing CCC, CNC, CNS, NNN, NCN, PCP, PNP, PCN, OCO, SCS, SNS, or SPS chelate. Matching seat. In some embodiments, the catalytic cobalt complex is not a cobalt-clamped complex containing NNN or NPN chelate ligands. In some embodiments, the catalytic cobalt complex is not one of the following:

In some embodiments, the catalytic cobalt complex is not a cobalt chelate complex. For example, the catalytic cobalt complex may comprise a cobalt-clamped complex containing a bidentate ligand, such as a complex defined by the formula below.

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 2, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4 , R ⁶ is selected from those in one of the following:

R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl.

In some embodiments, the catalytic cobalt complex can comprise a cobalt complex containing only a single tooth ligand. For example, the catalytic cobalt complex can comprise Py ₂ Co(CH ₂ SiMe ₃ ) ₂ .

In some embodiments, the catalytic cobalt complex can comprise a multimetallic cobalt complex, such as a bridged dicobalt complex. For example, the catalytic cobalt complex may comprise [(Cp*Co) ₂ -μ-(η ⁴ :η ⁴ -toluene)].

Also provided is an oxyborylation process for an aromatic compound having a ring substituent comprising at least one hydrogen atom at the alpha position of the aromatic ring, such as at least two hydrogen atoms Substituted by an atom or three hydrogen atoms. The method can include contacting the aromatic matrix with a catalytic cobalt complex and an oxonylating agent under conditions effective for oxyborylation of the carbon atom at the alpha position of the aromatic ring.

For example, a method for preparing an oxyborylation compound as defined by Formula VII is provided

Wherein X is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and Y is a boric acid or a boronic acid derivative. The method can include providing an aromatic matrix comprising a methyl substituted aryl group or a methyl substituted heteroaryl group, and rendering the aromatic matrix under conditions effective to form a compound defined by formula VII Contact with a catalytic cobalt complex and an oxyborylation reagent.

The aromatic matrix can comprise any suitable methyl substituted aryl or methyl substituted heteroaryl. The aryl or heteroaryl group may optionally further comprise one or more substituents other than the methyl substituent. Thus, X can be any suitable substituted or unsubstituted aryl or heteroaryl group. For example, X can be a substituted or unsubstituted aryl group (eg, a substituted or unsubstituted phenyl group). In other examples, X can be a substituted or unsubstituted heteroaryl group (eg, a substituted or unsubstituted pyridyl group).

In some embodiments, the aromatic matrix can comprise a compound defined by formula VIII

Wherein A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C ₆ alkyl group, C ₁ -C ₆ Haloalkyl, or a boronic acid or boronic acid derivative, each of R ¹ , R ² and R ³ being independently, hydrogen or C ₁ -C ₆ alkyl, and R ⁴ is independently present at each occurrence The ground is hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl.

In these specific examples, the oxyborylated aromatic compound may comprise a compound defined by formula IX

Wherein A is as described above at each occurrence, and Y is a boric acid or a boronic acid derivative. In certain instances, the oxyborylated aromatic compound can comprise a compound defined by Formula IX, wherein Y is a boronic acid derivative selected from one of the group consisting of:

In such methods, the catalytic cobalt complex can be any suitable cobalt (I) or cobalt (II) complex that catalyzes the C-H activated oxyborylation of the aromatic matrix. In some embodiments, the catalytic cobalt complex is a cobalt (II) complex.

In some embodiments, the catalytic cobalt complex can comprise a cobalt-clamping complex containing a tridentate ligand. For example, the catalytic cobalt complex can be a cobalt chelate complex. In some examples, the catalytic cobalt complex can be a cobalt-clamped complex containing CCC, CNC, CNS, NNN, NCN, PCP, PNP, PCN, OCO, SCS, SNS, or SPS chelate. Matching seat. In some embodiments, the catalytic cobalt complex is not a cobalt-clamped complex containing NNN or NPN chelate ligands. In some embodiments, the catalytic cobalt complex is not one of the following:

In some embodiments, the catalytic cobalt complex is not a cobalt chelate complex. For example, the catalytic cobalt complex may comprise a cobalt-clamping complex containing a bidentate ligand, such as a complex as defined by the following formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 2, and R ⁵ is independently, on each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, The R ⁶ is selected from one of the following:

R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl.

In some embodiments, the catalytic cobalt complex can comprise a cobalt complex containing only a single tooth ligand. For example, the catalytic cobalt complex can comprise Py ₂ Co(CH ₂ SiMe ₃ ) ₂ .

In some embodiments, the catalytic cobalt complex can comprise a multimetallic cobalt complex, such as a bridged dicobalt complex. For example, the catalytic cobalt complex may comprise [(Cp*Co) ₂ -μ-(η ⁴ :η ⁴ -toluene)].

The oxyborylation reagent used in the method as described above may be any suitable HB or B-B organic compound known in the art as an oxyborylation reagent. Suitable oxyborylation reagents can be selected in consideration of various factors, including consideration of the desired reactivity with respect to the resulting oxyborated aromatic hydrocarbon. Exemplary oxyborylation reagents include the HB or B-B organic compounds shown below.

In some embodiments, the oxyborylation reagent is selected from the group consisting of pinacolborane (HBPin), catecholborane, bis(neopentyl glycol) diborate. (bis(neopentyl glycolato)diboron), bis(pinacolato)diboron(B ₂ Pin ₂ ), bis(vinyl glycolic acid) diborate (bis(hexylene glycolato) Diboron), and bis(catecholato) diboron. In some embodiments, the boronylation reagent is pinacolborane (HBPin) or bis(pinacolato) diboron (B ₂ Pin ₂ ).

Oxyborylation compounds prepared using the methods described herein can be used in additional chemical reactions, including cross-coupling reactions, such as Suzuki-type cross-coupling reactions. In some specific examples, described herein The method may further comprise contacting the boroborylated aromatic compound with a reactant, and a transition metal catalyst, the reactant being selected from the group consisting of aryl halides, aryl pseudohalides (aryl pseudohalide), vinyl halide and vinyl pseudohalide to cross-couple the borolated aromatic compound with the reactant.

Detailed description of the preferred embodiment definition

Unless otherwise specifically stated, terms used herein will have their meaning equivalent to the art. The organic moieties referred to in the definitions of the variables in the formulas described herein - like the term halogen - are collective terms of the independent roster of independent group members. The C _n -C _m of the prefix in each example represents the number of possible carbon atoms in the group.

As used herein, the term "alkyl" refers to a straight, branched, cyclic, first or second or tertiary hydrocarbon that is saturated, including those having from 1 to 6 carbon atoms. In some embodiments, the alkyl group will include C ₁ , C ₁ -C ₂ , C ₁ -C ₃ , C ₁ -C ₄ , C ₁ -C ₅ or C ₁ -C ₆ alkyl. Examples of C ₁ -C ₆ alkyl groups include, but are not limited to, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 - dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl 1-methylpropyl, 1-ethyl-2-methylpropyl, and the isomers thereof. C ₁ -C ₄ -alkyl may include, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, and , 1-dimethylethyl.

The alkyl group contains a "cyclic alkyl group" or "cycloalkyl" group, including those having a single or multiple condensed rings with from 3 to 6 carbon atoms. In some embodiments, the cycloalkyl group comprises a C ₄ -C ₆ or C ₃ -C ₄ cyclic alkyl group. Non-limiting examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The alkyl group may be unsubstituted or substituted by one or more moieties, for example, an alkyl group, a halo group, a haloalkyl group, a hydroxyl group, a carboxyl group, a decyl group, a decyloxy group, an amine group. , an alkyl- or dialkylamino group, a decylamino group, a nitro group, a cyano group, an azide group, a thiol group, or any other practicable functional group, excluding the synthetic methods described herein, whether or not Protected is also protected as needed, as will be known to those skilled in the art, for example, as taught by Greene et al., Protective Groups in Organic Synthesis , John Wiley and Sons, Third Edition, 1999. It is incorporated by reference.

As used herein, the term "haloalkyl" refers to an alkyl group as defined above, which is substituted with one or more halogen atoms. For example, C ₁ -C ₄ haloalkyl includes, but is not limited to, chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro Fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2 , 2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2, 2-trichloroethyl, pentafluoroethyl and the like.

The term "alkoxy", also defined as -OR, wherein R is alkyl, refers to -O-alkyl, wherein alkyl is as defined above. Likewise, the term haloalkoxy can be used to refer to -O-haloalkyl, wherein haloalkyl is as defined above. In some embodiments, the alkoxy group can include from 1 to 6 carbon atoms. Examples of C ₁ -C ₆ -alkoxy include, but are not limited to, methoxy, ethoxy, C ₂ H ₅ -CH ₂ O-, (CH ₃ ) ₂ CHO-, n-butoxy, C ₂ H _5- CH(CH ₃ )O-, (CH ₃ ) ₂ CH-CH ₂ O-, (CH ₃ ) ₃ CO-, n-pentyloxy, 1-methylbutoxy, 2-methylbutoxy , 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-Hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutoxy, 1,2 - dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy , 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1 -methylpropoxy, and 1-ethyl-2-methylpropoxy.

The terms "alkylamino" and "dialkylamino" mean alkyl-NH- and (alkyl) ₂ N-, wherein alkyl is as defined above. Similarly, the term haloalkoxy group means a dialkylamino halo and haloalkyl and -NH- (haloalkyl) ₂ -NH-, wherein haloalkyl is as defined above system. The term "aminoalkyl" refers to an alkyl group as defined above which is substituted with an amine group.

The terms "alkylcarbonyl", "alkoxycarbonyl", "alkylaminocarbonyl" And "dialkylaminocarbonyl" means -C(=O)-alkyl, -C(O)-alkoxy, -C(O)-alkylamino, and -C(O)-dialkylamine. A group wherein the alkyl group, the alkoxy group, the alkylamino group, and the dialkylamine group are as defined above.

As used herein, the term "boric acid" refers to the -B(OH) ₂ moiety. The term boric acid derivative means a boron-containing moiety different from boric acid due to the presence or absence of one or more atoms, functional groups, or sub-structures, and the like may be imagined, at least in theory, via boric acid. Formed by chemical or physical methods. Examples of boric acid derivatives include boronic acid esters, also known as boronate, boronate esters, or boronic esters; aminoboranes And includes cyclic amino boronic esters such as 1,3,2-diazaborolidyl groups; and boric anhydride. The term boronic acid esters refers to an esterified boronic acid moiety, such as -B(OR) ₂ , wherein R is an alkyl group as defined above, and the cyclic boronic acid moiety is derived from -B(OR) ₂ Representing wherein the two R substituents are linked together to form a C ₂ -C ₆ cyclic moiety, which optionally includes one or more additional heteroatoms (eg, N, O, S, or And the like, and optionally further substituted with one or more substituents and/or fused to one or more additional carbocyclic or heterocarbocyclic groups (shared at least one bond). Examples of cyclic borate esters include, but are not limited to, pinanediol boronic esters, pinacol boronic esters, 1,2-ethaneborate, 1 , 3-propanediol borate, 1,2-propanediol borate, 2,3-butanediol borate, 1,1,2,2-tetramethylglycol borate, 1,2- Diisopropylethylene glycol borate, 5,6-nonanediol borate, 1,2-dicyclohexylethylene glycol borate, dicyclohexyl-1,1'-diol borate, Diethanolamine borate, and 1,2-diphenyl-1,2-ethaneborate.

As used herein, the term "halogen" refers to fluorine, chlorine, bromine and iodine atoms. The halo-(halo-) of the prefix (for example, as the term haloalkyl is used) refers to the full degree of halo substitution, from single substitution to perhalo substitution (for example, when stated as methyl, such as chloromethyl) (-CH ₂ Cl), dichloromethyl (-CHCl ₂ ), trichloromethyl (-CCl ₃ )).

The term "aromatic compound" as used herein generally refers to an aromatic ring or a plurality of aromatic rings fused together. Examples of the aromatic compound include, for example, benzene, naphthalene, anthracene, and the like. The term aromatic compound also includes heteroaromatic compounds (i.e., one or more of the aromatic ring carbon atoms have been replaced by an aromatic compound such as a hetero atom of O, N or S). Examples of the heteroaromatic compound include, for example, pyridine, furan, hydrazine, benzimidazole, thiophene, benzothiophene, and the like.

As used herein, the term "aryl" refers to a monovalent aromatic carbocyclic group of 6 to 14 carbon atoms. The aryl group can include a single ring or multiple condensed rings. In some embodiments, the aryl group includes a C ₆ -C ₁₀ aryl group. Aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, tetrahydronaphthyl, phenylcyclopropyl, and hydroquinone. The aryl group may be unsubstituted or substituted with one or more moieties selected from the group consisting of halogen, cyano, nitro, hydroxy, thiol, amine, alkyl, alkenyl, Alkynyl, cycloalkyl, cycloalkenyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, halocycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, Haloalkenyloxy, haloalkoxy, cycloalkoxy, cycloalkenyloxy, halocycloalkoxy, halocycloalkenyloxy, alkylthio, haloalkylthio, cycloalkylthio, halo Cycloalkylthio, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, haloalkylsulfinyl, haloalkylsulfinyl, haloalkynylenesulfinyl Alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, haloalkylsulfonyl, haloalylsulfonyl, haloalkynyl-sulfonyl, alkylamino, alkenylamino An alkynylamino group, a di(alkyl)amino group, a di(alkenyl)amino group, a bis(alkynyl)amino group, or a trialkyldecyl group.

As used herein, the term "heteroaryl" refers to a monovalent aromatic group of from 1 to 15 carbon atoms (eg, from 1 to 10 carbon atoms, from 2 to 8 carbon atoms, 3 to 6 carbon atoms, or 4 to 6 carbon atoms), having one or more heteroatoms in the ring. The heteroaryl group may include from 1 to 4 heteroatoms, from 1 to 3 heteroatoms, or from 1 to 2 heteroatoms. In some examples, the heteroatoms contained within the ring are oxygen, nitrogen, sulfur, or combinations thereof. When present, nitrogen or sulfur heteroatoms can be selectively oxidized. The heteroaryl group can have a single ring (e.g., pyridyl or furyl) or multiple fused rings, provided that the attachment is through a heteroaryl ring atom. Preferred heteroaryl groups include pyridyl, fluorene Base, pyrimidinyl, pyridyl Base, three Base, pyrrolyl, fluorenyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, furyl, phenylthio, furyl, imidazolyl, Azolyl, different Azolyl, isothiazolyl, pyrazolyl, benzofuranyl, and benzophenylthio. The heteroaryl ring can be unsubstituted or substituted with one or more moieties of an aryl group as described above.

method

A method for preparing an oxyborylated aromatic compound is provided. use The method for preparing an oxyborylated aromatic compound may comprise contacting an aromatic matrix with a catalytic cobalt complex and an oxyborylating agent under conditions effective to form the borolated aromatic compound.

The aromatic matrix can be any suitable aromatic matrix capable of undergoing C-H activated oxyborylation. For example, the aromatic matrix can be a substituted or unsubstituted aryl compound (eg, substituted or unsubstituted benzene), a substituted or unsubstituted six-membered heteroaromatic matrix (eg, , substituted or unsubstituted pyridine), or substituted or unsubstituted five-membered heteroaromatic matrix (eg, substituted or unsubstituted pyrrole, substituted or unsubstituted furan) Or a substituted or unsubstituted thiophene).

In some examples, the aromatic matrix can comprise a benzene ring. For example, the aromatic matrix can comprise a compound defined by Formula I.

Wherein A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C ₆ alkyl group, C ₁ -C ₆ Haloalkyl, or a boronic acid or boronic acid derivative, each of R ¹ , R ² and R ³ being independently, hydrogen or C ₁ -C ₆ alkyl, and R ⁴ is independently present at each occurrence The ground is hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl.

In these specific examples, the oxyborylated aromatic compound may comprise a compound defined by Formula II.

Wherein A is as described above at each occurrence, and Y is a boric acid or a boronic acid derivative. In certain instances, the oxyborylated aromatic compound can comprise a compound defined by Formula II, wherein Y is a boronic acid derivative selected from one of the group consisting of:

In some examples, the aromatic matrix can comprise a six member heteroaromatic compound. In some examples, the aromatic matrix can comprise a six-membered heteroaromatic defined by one of Formula IIIa, Formula IIIb, or Formula IIIc.

Wherein A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C ₆ alkyl group, C ₁ -C ₆ Haloalkyl, or a boronic acid or boronic acid derivative, each of R ¹ , R ² and R ³ being independently, hydrogen or C ₁ -C ₆ alkyl, and R ⁴ is independently present at each occurrence The ground is hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl.

In these specific examples, the oxyborylated aromatic compound may comprise a compound defined by one of Formula IVa, Formula IVb, or Formula IVc.

Wherein A is as described above at each occurrence, and Y is a boric acid or a boronic acid derivative. In certain instances, the oxyborylated aromatic compound can comprise a compound defined by Formula IVa, Formula IVb, or Formula IVc, wherein Y is a boronic acid derivative selected from one of the group consisting of:

In some examples, the aromatic matrix can comprise a five-membered heteroaromatic compound. In some examples, the aromatic matrix can comprise a five-membered heteroaromatic defined by one of Formula Va or Formula Vb.

Wherein X is NH, O, or S; A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C _{a 6} alkyl group, a C ₁ -C ₆ haloalkyl group, or a boronic acid or a boronic acid derivative, each of which R ¹ , R ² and R ³ are independently, hydrogen or C ₁ -C ₆ alkyl, And R ⁴ is independently, on each occurrence, hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl.

In these specific examples, the oxyborylated aromatic compound may comprise a compound defined by one of Formula VIa or Formula VIb.

Wherein A is as described above at each occurrence, and Y is a boric acid or boric acid derivative. In certain instances, the oxyborylated aromatic compound can comprise a compound defined by Formula VIa or Formula VIb, wherein Y is a boronic acid derivative selected from one of the group consisting of:

The percent conversion of the aromatic matrix to the boron boronated aromatic compound will vary depending on a number of factors, including the reactivity of the aromatic matrix, the bulk of the catalytic cobalt complex, and the bulk of the boron boronation reagent. Yu Yi In some embodiments, the percent conversion of the aromatic matrix to the oxyborylated aromatic compound can be at least 30% (eg, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%). , at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%).

The above method for forming an oxyborylated aromatic compound may comprise contacting the aromatic substrate to be reacted with a catalytic cobalt complex and an oxyborylating agent. The aromatic matrix can be contacted with the catalytic cobalt complex and the boron boronation reagent in any suitable manner such that the aromatic matrix and the boronylation reagent are catalytically effective amounts of the catalytic cobalt. A combination of complex compounds is present. For example, the aromatic matrix, the catalytic cobalt complex, and the borolylation reagent can be combined in a single reaction vessel or solution by any order or manner (eg, by sequential or simultaneous addition) The aromatic matrix, the catalytic cobalt complex and the borohydride reagent are introduced into a reaction vessel, and the aromatic matrix is contacted with the catalytic cobalt complex and the borohydride reagent. In some embodiments, the aromatic matrix can be contacted with the catalytic cobalt complex and the borohydride reagent at a temperature greater than 25 ° C to 85 ° C.

The catalytic cobalt complex can be any suitable cobalt (I) or cobalt (II) complex that catalyzes the C-H activated oxyborylation of the aromatic matrix. In some embodiments, the catalytic cobalt complex is a cobalt (I) complex.

In some embodiments, the catalytic cobalt complex can comprise a cobalt-clamping complex containing a tridentate ligand. For example, the catalytic cobalt complex can be a cobalt chelate complex. In some examples, the catalytic cobalt complex can be a cobalt-clamped complex containing CCC, CNC, CNS, NNN, NCN, PCP, PNP, PCN, OCO, SCS, SNS, or SPS chelate. Matching seat. In some embodiments, the catalytic cobalt complex is not a cobalt-clamped complex containing NNN or NPN chelate ligands. In some embodiments, the catalytic cobalt complex is not one of the following:

In some embodiments, the catalytic cobalt complex is not a cobalt chelate complex.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, _ n is 0, 1, 2, or 3, and E is -CH ₂ -, -C (R ¹⁰ ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently, each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , a nitrile group, a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and R ⁷ is independently, in each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ independently at each occurrence That is, C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ^{10 are} , independently of each occurrence, a C ₁ -C ₆ alkyl or aryl group.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, _n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane a radical, R ^{9 ,} at each occurrence, is independently C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, in each occurrence, C ₁ -C ₆ alkyl, Or aryl.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and R ⁷ is independently, in each occurrence, hydrogen or C. ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, _n is 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ⁷ is independently, on each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, Hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, _n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and R ⁷ is independently, in each occurrence, hydrogen or C. ₁ -C ₆ alkyl, when R ⁸ at each occurrence is independently, ^{hydrogen, -OR 7, -NR 7 R 7} , or C ₁ -C ₆ alkyl, R ⁹ at each occurrence is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane group, and R ¹⁰ at each occurrence is independently, C ₁ -C ₆ alkyl or aryl.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein at each occurrence Z is independently, a halide, C ₁ -C ₆ alkyl group, or aryl group, n is 0, 1, or 3, R ⁵ at each occurrence is independently, halo, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ or C ₁ -C ₆ alkyl, and R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring, which is selectively 1 Substituted to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group , or a C ₁ -C ₆ haloalkyl group.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, ^{-OR 7, -NR 7 R 7,} -C (= O) R 8, nitrile, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 2, 3, or 4, B is -P(R ⁹ ) ₂ , -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ⁷ is independently, on each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ at each occurrence is independently hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently at each occurrence, C ₁ -C ₆ alkyl , aryl, or -OR ¹⁰ , R ¹⁰ is independently, in each occurrence, a C ₁ -C ₆ alkyl or aryl group, and R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , a nitrile group, a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and The attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C( = O) R ^8, nitrile, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkoxy , And R ¹³ and R ¹⁴ are each independently selected from the Department, hydrogen, ^{halogen, -OR 7, -NR 7 R 7} , -C (= O) R 8, nitrile, C ₁ -C ₆ alkyl group, an aryl group Or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents, the substituent Department independently selected from ^{halo, -OR 7, -NR 7 R 7} , -C (= O) R 8, nitrile, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein at each occurrence Z is independently, a halide, C ₁ -C ₆ alkyl group, or aryl group, n is 0, 1, or 3, B is _{^{-P (R 9) 2, -OR}} 10 Or -NR ¹⁰ R ¹⁰ , R ⁹ is independently at each occurrence, C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , R ¹⁰ is independently, on each occurrence, C ₁ -C ₆ alkyl or aryl, R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ An alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring which is optionally substituted by 1 to 4 substituents Substituted, the substituent is independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl, and R ¹³ and R ¹⁴ are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkane a aryl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted by from 1 to 4 substituents The substituent is independently selected from halogen, -O R ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, R ¹⁵ and R ¹⁶ systems are each independently Selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group Or R ¹⁵ and R ^{16 together} with their attached carbon atoms form a benzene ring which is optionally substituted by from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ^7, when -C (= O) R ^8, nitrile, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, R ⁷ is independently in each occurrence, , hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is, independently of each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl.

In some embodiments, the catalytic cobalt complex can comprise a cobalt-clamping complex containing a bidentate ligand. For example, in some embodiments, the catalytic cobalt complex may comprise a complex as defined by the following formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 2, and R ⁵ is independently, on each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, The R ⁶ is selected from one of the following:

R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl.

In some embodiments, the catalytic cobalt complex can comprise a cobalt complex containing only a single tooth ligand. For example, the catalytic cobalt complex can comprise Py ₂ Co(CH ₂ SiMe ₃ ) ₂ . In some embodiments, the catalytic cobalt complex can comprise an N-heterocyclic carbene-ligated cobalt complex.

In some embodiments, the catalytic cobalt complex can comprise a multimetallic cobalt complex, such as a bridged dicobalt complex. For example, the catalytic cobalt complex may comprise [(Cp*Co) ₂ -μ-(η ⁴ :η ⁴ -toluene)].

The method can involve contacting the aromatic matrix with any catalytically effective amount of the catalytic cobalt complex. In some examples, the aromatic matrix may be mismatched from 0.5 mole percent (mol%) to 5.0 mole percent of the catalytic cobalt based on the number of moles of the aromatic matrix present in the boron boronation reaction. The material (for example, 1.0 mol% to 3.0 mol%) is contacted.

The oxyborylation reagent can be any suitable HB or B-B organic compound known in the art as an oxyborylation reagent. Suitable oxyborylation reagents can be selected in consideration of various factors, including consideration of the desired reactivity with respect to the resulting oxyborated aromatic hydrocarbon. Exemplary oxyborylation reagents include the HB or B-B organic compounds shown below.

In some embodiments, the oxyborylation reagent is selected from the group consisting of pinacolborane (HBPin), catecholborane, bis(neopentyl glycol) diborate. (bis(neopentyl glycolato)diboron), bis(pinacolato)diboron(B ₂ Pin ₂ ), bis(vinyl glycolic acid) diborate (bis(hexylene glycolato) Diboron), and bis(catecholato) diboron. In some embodiments, the boronylation reagent is pinacolborane (HBPin) or bis(pinacolato) diboron (B ₂ Pin ₂ ).

The boron boronation reagent can be incorporated into the boron boronation reaction in any suitable amount. For example, in some embodiments, the amount of the oxyborylation reagent present in the oxyborylation reaction may fall within a range of 1 mole per mole of aromatic matrix present in the oxyborylation reaction. An equivalent of an oxyborylation reagent, the molar base per mole of the aromatic matrix present in the boron boronation reaction is 5 molar equivalents of an oxyborylation reagent (eg, per mole present in the oxonylation reaction) The aromatic matrix is a 1 molar equivalent of oxyborylation reagent, and the molar base per mole of aromatic matrix present in the oxyborylation reaction is 3 mole equivalents of oxyborylation reagent).

Also provided is an oxyborylation process for an aromatic compound having a ring substituent comprising at least one hydrogen atom at the alpha position of the aromatic ring, such as at least two hydrogen atoms Substituted by an atom or three hydrogen atoms. The method can include contacting the aromatic matrix with a catalytic cobalt complex and an oxonylating agent under conditions effective for oxyborylation of the carbon atom at the alpha position of the aromatic ring.

For example, a method for preparing an oxyborylation compound as defined by Formula VII is provided

Wherein X is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and Y is a boric acid or a boronic acid derivative. The method can include providing an aromatic matrix comprising a methyl substituted aryl group or a methyl substituted heteroaryl group; and allowing the aromatic matrix to be formed under conditions effective to form a compound of formula VII Contact with a catalytic cobalt complex and an oxyborylation reagent.

The aromatic matrix can comprise any suitable methyl substituted aryl or methyl substituted heteroaryl. The aryl or heteroaryl group may optionally further comprise one or more substituents other than the methyl substituent. Thus, X can be any suitable substituted or unsubstituted aryl or heteroaryl group. For example, X may be a substituted or unsubstituted aryl group such as substituted or unsubstituted phenyl, biphenyl, naphthyl, tetrahydronaphthyl, phenylcyclopropyl or It is a hydroquinone group. In other examples, X may be a substituted or unsubstituted heteroaryl group, such as a substituted or unsubstituted pyridyl group, hydrazine. Base, pyrimidinyl, pyridyl Base, three Base, pyrrolyl, fluorenyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, furyl, phenylthio, furyl, imidazolyl, Azolyl, different Azolyl, isothiazolyl, pyrazolylbenzofuranyl, or benzophenylthio. In certain embodiments, X is a substituted or unsubstituted phenyl group or a substituted or unsubstituted pyridyl group.

In some embodiments, the aromatic matrix is a methyl substituted aryl compound. The methyl-substituted aryl compound may optionally further comprise one or more substituents other than the methyl substituent. For example, the aromatic matrix may comprise a compound defined by formula VIII

Wherein A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C ₆ alkyl group, C ₁ -C ₆ Haloalkyl, or a boronic acid or boronic acid derivative, each of R ¹ , R ² and R ³ being independently, hydrogen or C ₁ -C ₆ alkyl, and R ⁴ is independently present at each occurrence The ground is hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl.

In these specific examples, the oxyborylated aromatic compound may comprise a compound defined by formula IX.

Wherein A is as described above at each occurrence, and Y is a boric acid or boric acid derivative. In certain instances, the oxyborylated aromatic compound can comprise a compound defined by Formula IX, wherein Y is a boronic acid derivative selected from one of the group consisting of:

The percent conversion of the aromatic matrix to the boron boronated aromatic compound will vary depending on a number of factors, including the reactivity of the aromatic matrix, the bulk of the catalytic cobalt complex, and the bulk of the boron boronation reagent. In some embodiments, the percent conversion of the aromatic matrix to the oxyborylated aromatic compound can be at least 30% (eg, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%) %, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%).

The above method for forming an oxyborylated aromatic compound may comprise contacting the aromatic substrate to be reacted with a catalytic cobalt complex and an oxyborylating agent. The aromatic matrix can be contacted with the catalytic cobalt complex and the boron boronation reagent in any suitable manner such that the aromatic matrix and the boron boronation reagent are combined to catalyze an effective amount The catalytic cobalt complex is present. For example, the aromatic matrix, the catalytic cobalt complex, and the borolylation reagent can be combined in a single reaction vessel or solution by any order or manner (eg, by sequential or simultaneous addition) The aromatic matrix, the catalytic cobalt complex and the borohydride reagent are introduced into a reaction vessel, and the aromatic matrix is contacted with the catalytic cobalt complex and the borohydride reagent. In some embodiments, the aromatic matrix can be contacted with the catalytic cobalt complex and the borohydride reagent at a temperature greater than 25 ° C to 85 ° C.

The catalytic cobalt complex can be any suitable cobalt (I) or cobalt (II) complex that catalyzes the C-H activated oxyborylation of the aromatic matrix. In some embodiments, the catalytic cobalt complex is a cobalt (II) complex.

In some embodiments, the catalytic cobalt complex can comprise a cobalt-clamping complex containing a tridentate ligand. For example, the catalytic cobalt complex can be a cobalt chelate complex. In some examples, the catalytic cobalt complex can be a cobalt-clamped complex containing CCC, CNC, CNS, NNN, NCN, PCP, PNP, PCN, OCO, SCS, SNS, or SPS chelate. Matching seat. In some embodiments, the catalytic cobalt complex is not a cobalt-clamped complex containing NNN or NPN chelate ligands. In some embodiments, the catalytic cobalt complex is not one of the following:

In some embodiments, the catalytic cobalt complex is not a cobalt chelate complex.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ^{10 are} , independently of each occurrence, C ₁ -C ₆ alkyl or aryl.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane group, R ⁹ at each occurrence is independently, C ₁ -C ₆ alkyl group, an aryl group, or -OR ^10, and R ¹⁰ at each occurrence is independently, C ₁ -C ₆ alkyl, or Aryl.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and R ⁷ is independently, in each occurrence, hydrogen or C. ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ⁷ is independently, on each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, Hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane group, and R ¹⁰ at each occurrence is independently, C ₁ -C ₆ alkyl or aryl.

In some of these specific examples, E may be selected from -CH ₂ - and -C(R ¹⁰ ) ₂ -, wherein R ¹⁰ is as defined above.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ or C ₁ -C ₆ alkyl, and R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring, which is selectively 1 Substituted to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group , or a C ₁ -C ₆ haloalkyl group.

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, B is -P(R ⁹ ) ₂ , -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ⁷ is independently, on each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ at each occurrence is independently hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently at each occurrence, C ₁ -C ₆ alkyl , aryl, or -OR ¹⁰ , R ¹⁰ is independently at each occurrence, C ₁ -C ₆ alkyl, or aryl, R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, - OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and The attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C (=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl And the R ¹³ and R ¹⁴ are each independently selected from the group consisting of hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aromatic a group, or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents, the substitution The base is independently selected from the group consisting of halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group. .

In some embodiments, the catalytic cobalt complex may comprise a complex defined by the formula

Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and B is -P(R ⁹ ) ₂ , -OR ¹⁰ Or -NR ¹⁰ R ¹⁰ , R ⁹ is independently at each occurrence, C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , R ¹⁰ is independently, on each occurrence, C ₁ -C ₆ alkyl or aryl, R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ An alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring which is optionally substituted by 1 to 4 substituents Substituted, the substituent is independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl, and R ¹³ and R ¹⁴ are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkane a aryl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted by from 1 to 4 substituents The substituent is independently selected from halogen, - OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, R ¹⁵ and R ¹⁶ systems are each independently Selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group Or R ¹⁵ and R ^{16 together} with their attached carbon atoms form a benzene ring which is optionally substituted by from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, R ⁷ is independently , hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is, independently of each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl.

In some embodiments, the catalytic cobalt complex can comprise a cobalt-clamping complex containing a bidentate ligand. For example, in some embodiments, the catalytic cobalt complex may comprise a complex as defined by the following formula

Wherein at each occurrence Z is independently, a halide, C ₁ -C ₆ alkyl group, or aryl group, n is is 2, R ⁵ at each occurrence is independently, halogen, -OR ^7, -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, The R ⁶ is selected from one of the following:

R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl.

In some embodiments, the catalytic cobalt complex can comprise a cobalt complex containing only a single tooth ligand. For example, the catalytic complexes may comprise cobalt _{Py 2 Co (CH 2 SiMe 3} ) 2.

In some embodiments, the catalytic cobalt complex can comprise a bridged dicobalt complex. For example, the catalytic cobalt complex may comprise [(Cp*Co) ₂ -μ-(η ⁴ :η ⁴ -toluene)].

The method can involve making the aromatic compound effective with any catalyst The amount of the catalytic cobalt complex is contacted. In some examples, the aromatic compound may be from 0.5 mol% to 5.0 mol% of the catalytic cobalt complex (for example, 1.0) based on the molar number of the aromatic compound present in the boron boronation reaction. Mol% to 3.0 mol%) contact.

The oxyborylation reagent can be any suitable HB or B-B organic compound known in the art as an oxyborylation reagent. Suitable oxyborylation reagents can be selected in consideration of various factors, including consideration of the desired reactivity with respect to the resulting oxyborated aromatic hydrocarbon. Exemplary oxyborylation reagents include the HB or B-B organic compounds shown below.

In some embodiments, the boronylation reagent is selected from the group consisting of pinacolborane (HBPin), catecholborane, bis(neopentyl glycol) diborate. (bis(neopentyl glycolato)diboron), bis(pinacolato)diboron(B ₂ Pin ₂ ), bis(vinyl glycolic acid) diborate (bis(hexylene glycolato) Diboron), and bis(catecholato) diboron. In certain embodiments, the reagent is a boron-based oxide materials can be satisfied borane (pinacolborane) (HBPin) or bis (Perpignan alcohol) diboronate (bis (pinacolato) diboron) ( B 2 Pin 2).

The boron boronation reagent can be incorporated into the boron boronation reaction in any suitable amount. For example, in some embodiments, the amount of the oxyborylation reagent present in the oxyborylation reaction may fall within a range of 1 mole per mole of aromatic matrix present in the oxyborylation reaction. An equivalent of an oxyborylation reagent, the molar base per mole of the aromatic matrix present in the boron boronation reaction is 5 molar equivalents of an oxyborylation reagent (eg, per mole present in the oxonylation reaction) The aromatic matrix is a 1 molar equivalent of oxyborylation reagent, and the molar base per mole of aromatic matrix present in the oxyborylation reaction is 3 mole equivalents of oxyborylation reagent).

The oxyborylated aromatics prepared using the methods described herein can be used in additional chemical reactions, including cross-coupling reactions, such as the Suzuki-type cross-coupling reaction. Suzuki type cross-coupling reactions are known in the art and can be used to cross-couple an organic halide and organoborane in the presence of a base and a suitable catalyst. See, for example, Miyaura, N.and Suzuki, A.Chem.Rev. 1995, 95, 2457, Stanforth, SP Tetrahedron 1998, 54, 263, Lipshutz et al., The Synthesis 2005, 2989, and the Organic Lipshutz et al. Letters 2008 , 10 , 4279. The organic halide may be an unsaturated halide or pseudohalid (for example, triflate (OTf)), an aryl halide or a pseudohalide, or a vinyl halide or a pseudohaloethylene ( Vinyl halide or pseudohalide).

In some embodiments, the methods described herein can further comprise contacting the boroborylated aromatic compound with a reactant, and a transition metal catalyst, the reactant being selected from the group consisting of: a base halide, an aryl pseudohalid, a vinyl halide, and an n vinyl pseudohalide to cross-couple the reactant with the boron boronated aromatic compound. As an example, (4-chloro-2-fluoro-3-substituted) borate can be combined with methyl 4-acetamido-3,6-dichloropyridinium (methyl 4-acetamido-3,6- Dichloropicolinate) A cross-coupling reaction is carried out to prepare or form 6-(4-chloro-2-fluoro-3-substituted-phenyl)-4-aminomethylpyridyl ester. In another example, the (4-chloro-2-fluoro-3-substituted) boronate can be combined with methyl 6-acetamido-2-chloropyrimidine-4-carboxylate or its unprotected The analog 6-amino-2-chloropyrimidine-4-carboxylic acid undergoes a cross-coupling reaction.

The Suzuki type cross-coupling reaction can occur in the presence of a palladium catalyst, a ligand, and a base. At least some embodiments, the palladium catalyst is palladium acetate (II) (Pd (OAc) 2), the base is aqueous potassium carbonate (K ₂ CO _3), and a seat with triphenylphosphine (PPh _3). The cross-coupling reaction can be carried out in a solvent such as methyl isobutyl ketone (MIBK), acetonitrile (MeCN), ethyl acetate (EtOAc), water, or a combination thereof.

Examples of certain specific examples of the disclosure provided below are provided as non-limiting illustrations.

Example Materials and Method

Unless otherwise stated, the reaction was carried out in a glass oven under magnetic stirring in an oven, under a nitrogen atmosphere, and monitored by proton nuclear magnetic resonance ( ¹ H-NMR) spectroscopy. Tetrahydrofuran was newly distilled from sodium/benzophenone under a nitrogen atmosphere. Py ₂ Co(CH ₂ SiMe ₃ ) ₂ and (Cp*Co) ₂ (η ⁴ :η ⁴ -toluene) were synthesized according to established literature procedures. Rapid or column chromatography was performed using tantalum (230-400 mesh) available from Silicycle (Quebec City, Canada). ¹ H NMR, ¹³ C NMR and ¹⁹ F NMR spectra were obtained using a 7600AS 96 sample autosampler equipped with VnmrJ 3.2A, Agilent DirectDrive 2 500 MHz NMR spectrometer (500 MHz for ¹ H NMR, 125 MHz for ¹³ C NMR, ¹⁹ The F NMR aspect was 470 MHz, and the ¹¹ B NMR aspect was 160 MHz) was recorded. The melting point was measured on a Thomas-Hoover capillary melting point apparatus.

Use Py ₂ Co(CH) ₂ SiMe ₃ ) ₂ Solvent screening as a catalyst

Py ₂ Co(CH ₂ SiMe ₃ ) ₂ (9.8 mg (mg), 0.025 mmol (mmol), 5 mol%) and m-xylene (306 μL (μL), 2.5) in a nitrogen-filled glove box Ment) Load into a 3 ml (mL) Wheaton® vial. A suitable solvent (1.0 mL) and HBPin (73 μL, 0.5 mmol) were added sequentially. The vial was closed and placed in an oil bath at 50 ° C outside the glove box and heated for 24 hours (h). The reaction was cooled to room temperature and the same was removed and analyzed by gas chromatography (GC). The results are shown in Table 1.

^a yield corrected GC yield.

Try using 3-trifluoromethyltoluene as a substrate

Py ₂ Co(CH ₂ SiMe ₃ ) ₂ (9.8 mg, 0.025 mmol, 5 mol%), 3-trifluoromethyltoluene (349 μL, 2.5 mmol) and HBPin (73 μL, 0.5 mmol) in a nitrogen-filled glove box ) Loaded sequentially into a 3 mL Wheaton® vial. The vial was closed, removed from the glove box, and stirred at room temperature. After 16 h, the sample was taken from the reaction mixture and analyzed by GC. No oxygen boronation product was observed.

Try to Py ₂ Co(CH) ₂ SiMe ₃ ) ₂ Oxyborylation of a bromine- and chlorine-containing substrate as a catalyst

Py ₂ Co(CH ₂ SiMe ₃ ) ₂ (9.8 mg, 0.025 mmol, 5 mol%), 3-tribromotoluene (303 μL, 2.5 mmol), and HBPin (73 μL, 0.5 mmol) in a nitrogen-filled glove box. Loaded into 3 mL Wheaton® vials in succession. The vial was closed, removed from the glove box, and heated at 50 °C. After 24 h, the sample was taken from the reaction mixture, and the gas chromatography-mass spectrometry (GC-MS) analysis of the sample showed a stoichiometric amount of boron boron based on the exchange of bromine and boron. Chemical product. When 2-chlorotoluene was used as the substrate, the chlorine-boron exchange product in the crude reaction mixture was observed by GC-MS.

Use (Cp*Co) ₂ (η ⁴ :η ⁴ -Toluene) as a catalyst for the concentration of oxyborylation of xylene between catalysts and concentration

(Cp*Co) ₂ (η ⁴ :η ⁴ -toluene) (12 mg, 0.025 mmol, 5 mol%) and B ₂ Pin ₂ (127 mg, 0.5 mmol) were charged into 3 mL of Wheaton® in a nitrogen-filled glove box. In the glass bottle. A suitable solvent (1.0 mL) and m-xylene (306 μL, 2.5 mmol) were added sequentially. The small glass bottle was closed, capped, taken out of the glove box, and heated at 80 ° C for 24 h. Thereafter, the reaction was cooled to room temperature, and a sample was taken from the reaction mixture for GC analysis. The results are shown in Table 2. It has been found that by increasing the concentration of the reactants, the conversion is increased, however, the selectivity to aromatic boronylation is lowered.

^a yield corrected GC yield. ^{The b} reaction was carried out for 18 h.

Use (Cp*Co) ₂ (η ⁴ :η ⁴ External ligand screening for the boronylation of m-xylene with toluene

(Cp*Co) ₂ (η ⁴ :η ⁴ -toluene) (12 mg, 0.025 mmol, 5 mol%), B ₂ Pin ₂ (127 mg, 0.5 mmol) and the following ligands in a nitrogen-filled glove box One of them was charged into a 3 mL Wheaton® vial: Ph ₃ P (6.6 mg, 0.025 mmol, 5 mol%), 4-(dimethylamino)pyridine (DMAP; 3.0 mg, 0.025 mmol, 5 mol%), 1 , 10-phenoline (phen; 2.2 mg, 0.0125 mmol, 2.5 mol%), Cyclohexylphosphine (Cy ₃ P; 7.0 mg, 0.025 mmol, 5 mol%), or pyridine (Py; 2.0 μL, 0.025 mmol, 5 mol%). Tetrahydrofuran (1.0 mL) and m-xylene (306 μL, 2.5 mmol) were successively added. The small glass bottle was closed, capped, taken out of the glove box, and heated at 80 ° C for 24 h. After the heating was completed, the reaction vial was cooled to room temperature, and the sample was taken out from the reaction mixture for GC analysis. The results are shown in Table 3.

^a yield corrected GC yield.

Oxyborylation of methyl 3-trifluoromethylbenzoate

(Cp*Co) ₂ (η ⁴ :η ⁴ -toluene) (12 mg, 0.025 mmol, 5 mol%) and B ₂ Pin ₂ (127 mg, 0.5 mmol) were charged into 3 mL of Wheaton® in a nitrogen-filled glove box. In the glass bottle. Tetrahydrofuran (0.5 mL) and methyl 3-trifluoromethylbenzoate (236 μL, 1.5 mmol) were added sequentially. The small glass bottle was closed, capped, taken out of the glove box, and heated at 80 ° C for 17 h. After the heating was completed, the reaction vial was cooled to room temperature, and the sample was taken for analysis. GC analysis showed the absence of the boron boronation product.

Use (Cp*Co) ₂ (η ⁴ :η ⁴ -Toluene) Oxyborylation of 3-trifluorotoluene

(Cp*Co) ₂ (η ⁴ :η ⁴ -toluene) (12 mg, 0.025 mmol, 5 mol%) and B ₂ Pin ₂ (127 mg, 0.5 mmol) were charged into 3 mL of Wheaton® in a nitrogen-filled glove box. In the glass bottle. Tetrahydrofuran (0.5 mL) and 3-trifluorotoluene (167 μL, 1.5 mmol) were successively added. The vial was capped, removed from the glove box, and heated at 80 ° C for 21 h. After the heating was completed, the reaction vial was cooled to room temperature, and the sample was taken for analysis. From the ¹⁹ F NMR spectrum, a 25% conversion (based on B ₂ Pin ₂ ) was observed. Determined by ¹⁹ F NMR spectroscopy, 2-(3-fluoro-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-di Pentaborane to 2-(2-fluoro-4-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-di The ratio of pentaborane is 1.4:1. 2-(3-Fluoro-5-tolyl)-4,4,5,5-tetramethyl-1,3,2-di Pentaborane: ¹⁹ F NMR (283MHz, CDCl ₃ ) δ -115.4. 2-(2-Fluoro-4-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-di Pentaborane: ¹⁹ F NMR (283 MHz, CDCl ₃ ) δ -103.8 - -103.9.

Using CoCl ₂ And external coligase screening of Zn for m-xylene boron boronation

The evaluation of various cobalt-based systems including phosphine- or nitrogen-containing ligands was carried out using the general procedure outlined in Scheme 1 for the oxyborylation of m-xylene oxyborylation. CoCl ₂ (6.5 mg, 0.05 mmol, 10 mol%), ligand (0.05 mmol, 10 mol%) and Zn powder (9.8 mg, 0.15 mmol, 30 mol%) were charged into 3 mL Wheaton® in a nitrogen-filled glove box. In a small glass bottle. Then 1.0 mL of THF was added. Meta-xylene (183 μL, 1.5 mmol) and boron source (0.5 mmol) were successively added to the resulting solution. The vial is then capped and removed from the glove box. The reaction mixture was heated at 80 ° C for 16-20 h. After heating, an aliquot was removed and analyzed by gas chromatography. In all of the examples, no products of oxyborylation were detected.

Oxyborylation using a cobalt complex containing a bidentate ligand

A cobalt complex comprising a bidentate ligand comprising both a pyridine moiety and an imine moiety was evaluated as a catalyst for oxyborylation. This type of ligand can be obtained by condensation of 2-pyridinecarboxaldehyde with a suitable aniline. Pyridine aniline-linked cobalt chloride complex 1-4 was prepared using the procedures of the literature. See, for example, Zhu, D. et al., Organometallics 2010 , 29 , 1897. All complexes are isolated as chloride bridged dimers. Chloride ligands can be substituted to activate these complexes for oxyborylation.

In the first experiment, the chloride ligand on cobalt complex 1 was substituted by reaction with LiCH ₂ TMS to form complex 5 . The complex 5 was then evaluated as a catalyst for the oxyborylation of meta-xylene. Complex 5 (11.1 mg, 0.025 mmol, 5 mol%) and m-xylene (183 μL, 1.5 mmol) were placed in a 3 mL Wheaton® vial in a nitrogen-filled glove box. HBPin (73 μL, 0.5 mmol) was added. The vial is capped and removed from the glove box. The reaction mixture was then heated at 50 ° C for 15 h. Analysis by gas chromatography showed a 29% conversion based on HBpin. Although complex 5 is catalytically active, long term storage is unstable.

Activation of complex 1-4 can also be accomplished using a reducing metal (eg, magnesium or zinc) to reduce the cobalt center and remove one or both of the chloride ligands.

In the initial experiments, the use of 2.5mol% of 1, 12mol% of Richter (Rieke's) Mg, and m-xylene 3eqiuv HBpin (1equiv) carried out at 50 ℃, no product was observed boryl group. However, the reaction was carried out in THF at 80 ° C to obtain 48% total conversion, and 41% was compound 6 . The observed ratio of benzyl to metal boron borylation was 27:1.

When the complex 3 was used as a catalyst under the same conditions, the GC detected a slightly lower total conversion (38%) (Scheme 3). Specifically, cobalt complex 3 (19.8 mg, 0.025 mmol, 2.5 mol%) and active Mg (2.4 mg, 0.1 mmol, 10 mol%) were charged into a 3 mL Wheaton® vial in a nitrogen-filled glove box. in. Then 0.5 mL of THF was added. The resulting mixture was stirred for 5 min. Meta-xylene (367 μL, 3.0 mmol) and HBpin (145 μL, 1.0 mmol) were successively added. The vial is capped and removed from the glove box. The reaction mixture was heated at 80 ° C for 16 h. Analysis by GC showed 38% conversion on a HBpin basis and 34% was identified as a benzyloxyboronation product 6 .

When zinc or Super-Hydride® (LiHBEt ₃ 1.0M in THF) was used instead of magnesium, no oxygen boronation product was observed. An iron (II) bromide analog of cobalt complex 3 was also prepared, and Rieke's Mg was used to test the activity in the boron boronation reaction. When a meta-xylene or 3-trifluorotoluene substrate was used, no oxygen boronation product was detected.

Flowchart 3. Oxyborylation of m-xylene using Rieke's Mg as an activator

The activation of complexes 1-4 was also investigated using a Grignard reagent. In the first experiment, the complex 1 and EtMgBr were evaluated as catalytic systems. The meta-xylene system was oxyborylated with a total conversion of 42%. Furthermore, the benzyloxyboronation product 6 was the major product and was detected by GC at 37% (Scheme 4). Unfortunately, the conversion rate changed from 0 to 42% during 3 operations.

Similar conditions were used to study the activation of cobalt complex 3 with various Grignard reagents. Cobalt Complex 3 (19.8 mg, 0.025 mmol, 2.5 mol%) was placed in a 3 mL Wheaton® vial in a nitrogen filled glove box. THF (0.5 mL) and m-xylene (367 μL, 3.0 mmol) were successively added. Then, a Grignard reagent (0.1 mmol, 10 mol%) was added dropwise. The resulting mixture was then stirred for approximately 5 min. Then HBpin (145 μL, 1.0 mmol) was added. The vial is capped and removed from the glove box. The reaction mixture was heated at 80 ° C for 21 h. After heating, an aliquot was removed and analyzed by gas chromatography. The results are included in Table 1 below.

When EtMgBr was used as the activator, significant variation was observed as a result of the boron boronation reaction. During the six operations, the conversion rate was varied from 31-92% (Table 1, item 2). CyMgCl provided a conversion rate of 79-92% during 5 runs (Table 1, item 4). In the two tests performed using MeMgCl as the activator, a conversion of 57-84% was observed (Table 1, item 1). The large tBuMgCl (bulky tBuMgCl) achieved low conversion, and when PhMgCl was used as the catalyst activator, no product of the boron boronation was observed.

Other organometallic reagents, such as Bu ₂ Mg or Et ₂ Zn, are also screened as potential reducing agents for use as activators of cobalt complex 3 . When diethylzinc was used as the catalyst activator, the product of the boron boronation was not detected by the GC. However, a 75% conversion of meta-xylene (62% benzyloxyboronated product 6 ) to the product of the oxyborylation was observed with di-n-butylmagnesium.

The activity of cobalt complex 4 (with a larger pyridyl aniline ligand) for the boron boronation of cobalt complex 3 in m-xylene was compared. The boron boronation reaction performed using Cobalt Complex 4 resulted in 63% total conversion, and 57% (Scheme 5) oxyborylation of Compound 6 was detected. However, cobalt complex 4 provides a lower conversion than Catalyst 3 . No significant differences were observed in terms of selectivity.

The amount of activator (e.g., Grignard reagent) and the order in which the reagent is added are found to affect the boron boronation reaction. It is assumed that if 5 or 20 mol% of a Grenadi reagent (for example, EtMgBr and CyMgCl) is used, the GC does not find an oxyborylation product. The order in which the reagents are added also affects the results of the reaction. In the reaction examples described in Table 1, the catalyst was first suspended in THF and m-xylene. The Grena reagent is then slowly added to the mixture. The resulting mixture was stirred for about 5 min; then HBpin was added to the reaction. Of course However, if the order of addition of the reagents is modified so that the reagent finally added to the reaction is a genomic reagent (after Hbpin), the overall reaction conversion is remarkably reduced (EtMgBr is 34%; CyMgCl is 13%). It has also been found that the addition of pyridine as an external ligand stops the reaction.

Discussion on the transfer of oxygen boronation machine

It is assumed that the boron boronation reaction proceeds by radical or ion machine. It is expected that the addition of a radical scavenger to the boronylation reaction should slow or stop the reaction if the boronylation reaction is carried out by a free radical machine.

The boronylation reaction is carried out in the presence of 1-octene and 9,10-dihydroanthracene (Scheme 6). When the olefin was present, GC-MS detected the addition hydroboration of 1-octene, and it was observed that the meta-xylene did not produce the boron boronation product. Likewise, when 9,10-dihydroanthracene was present, it was observed that meta-xylene did not produce an oxyborylation product. However, in this case, neither ruthenium (9,10-dihydroanthracene and the expected reaction product of the radical species) was detected by GC or GC-MS.

In order to better illustrate the reaction of the reactor, p-cymene is used as a substrate for oxyborylation. It is assumed that if the oxyborylation of dihydrocarbons is carried out by radical intermediates, we would expect to establish a balance of primary and tertiary radicals during the reaction. We will expect this to lead to Two oxyborylated products are formed.

In the first experiment, the oxyborylation of p-cymene was carried out using cobalt complex 3 and EtMgCl as activators. Cobalt Complex 3 (19.8 mg, 0.025 mmol, 2.5 mol%) was placed in a 3 mL Wheaton® vial in a nitrogen filled glove box. Then, THF (0.5 mL) and dihydrocarbene (468 μL, 3.0 mmol) were added. Then EtMgCl (2.0 M in MeTHF) (50 μL, 0.1 mmol) was added dropwise. The resulting mixture was then stirred for approximately 5 min. Then HBpin (145 μL, 1.0 mmol) was added. The vial is capped and removed from the glove box. The reaction mixture was heated at 80 ° C for 21 h. GC analysis showed that 19% was converted to a single isomer based on HBpin (Scheme 7). Performing this reaction using CyMgCl or MeMgCl as the activator did not provide the boron boronation product.

Then, a competitive experiment was performed, and the molar amount of meta-xylene and p-cymene were subjected to oxygen boronation in a competitive experiment (Scheme 8). Cobalt Complex 3 (19.8 mg, 0.025 mmol, 2.5 mol%) was placed in a 3 mL Wheaton® vial in a nitrogen filled glove box. THF (0.5 mL), m-xylene (367 μL, 3.0 mmol) and dioxane (468 μL, 3.0 mmol) were added. Then CyMgCl (1.0 M in MeTHF) (100 μL, 0.1 mmol) was added dropwise. The resulting mixture was then stirred for approximately 5 min. Then HBpin (145 μL, 1.0 mmol) was added. The vial is capped and removed from the glove box. The reaction mixture was heated at 80 ° C for 21 h. GC analysis showed 72% conversion of meta-xylene (based on HBpin) and 7% conversion of dihydrocarbon (based on HBpin).

The dihydrocarbon is a good hydrogen atom precursor which can be transferred via a hydrogen atom to form a stable equilibrium of the tertiary benzyl radical. In view of the fact that dioxane does not stop the oxyborylation of meta-xylene in competitive experiments, it is likely that such cobalt-catalyzed oxyborylation is not via a free radical route.

The fate of the alkyl residue from the Grena reagent was investigated using dodecylmagnesium bromide as the activator. Under the conditions of the catalytic reaction, traces of dodecane were detected by GC and GC-MS. An aliquot of the stoichiometric reaction from Cobalt Complex 3 and Dodecylmagnesium bromide was analyzed by GC to perform dodecane quantification. This stoichiometric reaction yield of 70% dodecane; however, GC-MS is also aware of other unidentified C ₁₂ of the product-containing.

Several other oxyborylated substrates have also been tried. When 4-methoxytoluene was used as the substrate, a trace amount of the product was observed by GC. No boron boronation product was observed with 3-fluorotoluene or 2,6-dimethylpyridine.

It is assumed that the boron boronation reaction involves the exchange of halide ligands in a cobalt complex having an alkoxy group. To investigate this possibility, meta-xylene was subjected to oxyborylation using cobalt complex 3 and KOtBu as activators. Cobalt Complex 3 (19.8 mg, 0.025 mmol, 2.5 mol%) and KOtBu (17 mg, 0.15 mmol) were placed in a 3 mL Wheaton® vial in a nitrogen-filled glove box. Then THF (0.5 mL) was added. The resulting mixture was then stirred for approximately 5 min. Then m-xylene (367 μL, 3.0 mmol) and B ₂ pin ₂ (254 mg, 1.0 mmol) were added. The vial is capped and removed from the glove box. The reaction mixture was heated at 80 ° C for 17 h. Analysis by GC showed 8% conversion of meta-xylene based on B ₂ pin ₂ and a ratio of benzyl to metal boronation product of 1:2 (Scheme 9). It was observed that HBpin did not respond. The conversion achieved by NaOtBu is similar. Other bases such as LiOtBu, K2CO3, K3PO4 and KOAc are inefficient.

Scheme 9. Oxyborylation of m-xylene using cobalt complex 3 and KOtBu as activator

Oxyborylation using a cobalt complex comprising N-heterocyclic carbene (NHC)

Evaluation of a cobalt complex containing a N-heterocyclic carbene (NHC) as a ligand as an oxygen boronation catalyst was carried out. Using CoCl ₂ as a source of cobalt, NHC-1 as a carbene precursor, and a base (KOtBu), an active cobalt catalyst can be formed in situ, and successful m-boroxylation of meta-xylene can be achieved (flow Figure 10).

Cobalt chloride (6.5 mg, 0.05 mmol, 5 mol%), 1,3-diisopropyl-1H-imidazol-3-indene chloride (1,3-diisopropyl-1H- in a glove box filled with nitrogen) Imidazol-3-ium chloride) (18.9 mg, 0.1 mmol) and KOtBu (22.4 mg, 0.2 mmol) were placed in a 3 mL Wheaton® vial. THF (0.5 mL) was added and the resulting mixture was stirred for approximately 10 min. A purple solution is formed. Next, m-xylene (367 μL, 3.0 mmol) and HBpin (145 μL, 3.0 mmol) were added. The vial is capped and removed from the glove box. The reaction mixture was then heated at 80 ° C for 16 h. GC analysis showed 40% conversion of meta-xylene based on HBpin. Under the same reaction conditions, B ₂ pin ₂ did not provide any product of boron boronation. Under the same reaction conditions, ethylbenzene provided 56% conversion of the starting material (45% conversion to benzyloxyboronated product).

Scheme 10. Meta-xylene using in situ formed carbene-linked cobalt complex

It is assumed that the active oxyborylation catalyst in the above reaction is an NHC-linked cobalt alkoxide formed in situ during the oxyborylation reaction. To test this hypothesis, the putative active oxyborylation catalyst ( NHC-1 ) was synthesized and isolated. Briefly, CoCl _{2 was} reacted with NHC-1 in the presence of a KotBu base to provide a cobalt catalyst 8 having a yield of 88% after recrystallization (Scheme 11).

A glove box filled with nitrogen, containing CoCl ₂ (168 mg, 1.3 mmol) and 1,3-diisopropyl-1H-imidazole-3-indene chloride (490 mg, 2.6 mmol), was placed in an oven-dried glassware. Then THF (8 mL) and KOtBu (583 mg, 5.2 mmol) were successively added. The resulting mixture was stirred in a glove box for 1 h. The solvent was then removed under vacuum and the residue was suspended in toluene and filtered through Celite®. The filtrate was collected and the solvent was removed in vacuo to afford 635 mg of dark purple crystalline material. At -35 ℃ recrystallized from pentane to provide 582mg (88%) of 8-cobalt complexes. Single crystal X-ray diffraction confirms the structure. ¹ H NMR (500 MHz, benzene-d6, ppm) δ 41.70 (s, 4H) 39.00 (br s, 4H) 8.76 (br s, 18H) 2.31 (br s, 24H).

Flowchart 11. Synthesis of Cobalt Catalyst 8

Cobalt complex 8 was then evaluated as an oxyborylation catalyst. Cobalt Complex 8 (5.1 mg, 0.01 mmol, 2 mol%) was placed in a 3 mL Wheaton® vial in a nitrogen filled glove box. Then THF (0.25 mL) and m-xylene (183 μL, 1.5 mmol) were added successively. Then HBpin (73 μL, 0.5 mmol) was added. The vial is capped and removed from the glove box. The reaction mixture was then heated at 80 ° C for 16 h. GC analysis showed 80% conversion of meta-xylene based on HBpin. 62% of the monoborylated product 6 was formed with 13% of the 偕-diBpin (gem-diBpin) product 9 .

In another experiment, the oxyborylation reaction was carried out using a substrate as a limiting reagent. Cobalt Complex 8 (10.2 mg, 0.02 mmol, 2 mol%) was placed in a 3 mL Wheaton® vial in a nitrogen-filled glove box. Then THF (0.25 mL) and m-xylene (122 μL, 1.0 mmol) were added. Then, HBpin (290 μL, 2.0 mmol) was added. The vial is capped and removed from the glove box. The reaction mixture was then heated at 80 ° C for 17 h. Analysis by GC showed 71% conversion of meta-xylene: 37% of the monoborylated product 6 was formed with 29% of the 偕-diBpin (gem-diBpin) product 9 and 5% of the unidentified diBpin product. .

It has also been found that if a catalytic amount of Hbpin is added to activate the cobalt precatalyst 8, B ₂ pin ₂ can be used as the primary source of boron. Cobalt Complex 8 (10.2 mg, 0.02 mmol, 2 mol%) was placed in a 3 mL Wheaton® vial in a nitrogen-filled glove box. THF (0.5 mL) and m-xylene (122 μL, 1.0 mmol) were added. Then, HBpin (11.6 μL, 0.08 mmol, 8 mol%) and B ₂ pin ₂ (381 mg, 1.5 mmol) were added. The vial is capped and removed from the glove box. The reaction mixture was then heated at 80 ° C for 16 h. Analysis by GC showed 77% conversion of meta-xylene: 31% of the monoborylated product 6 was formed with 40% of the gem-diBpin product 9 and 6% of the unidentified diBpin product. Extending the heating for up to 40 hours does not improve the conversion and product ratio. The isolation of the product was carried out on a silica gel using a pentane-diethyl ether mixture as a flash column for rapid column chromatography. 4,4,5,5-tetramethyl-2-(3-tolyl)-1,3,2-di The pentaborane was isolated as a colorless oil with a yield of 19%. _{^{1 H NMR (500MHz, CDCl 3}} , ppm) δ 7.14 (dd, 1H, J = 7.2,7.2Hz) 7.02-6.98 (m, 2H) 6.95 (d, 1H, J = 7.5Hz) 2.32 (s, 3H) 2.27 (s, 2H) 1.25 (s, 12H). ¹³ C NMR (125 MHz, CDCl ₃ , ppm) δ 138.4, 137.7, 129.8, 128.1, 125.9, 125.6, 83.4, 24.7, 21.4. No signal was found for a carbon. ¹¹ B NMR (160 MHz, CDCl ₃ , ppm) δ 33.0. 2,2'-(between Benzylmethyl)-bis(4,4,5,5-tetramethyl-1,3,2-di The pentaborane) is 21% yield. _{^{1 H NMR (500MHz, CDCl 3}} , ppm) δ 7.14-7.09 (m, 2H) 7.05 (s, 1H) 6.92-6.88 (m, 1H) 2.30 (s, 3H) 2.27 (s, 1H) 1.24 (s, 12H) 1.23 (s, 12H). ¹¹ B NMR (160 MHz, CDCl ₃ , ppm) δ 32.9.

Additional matrices were also evaluated. Oxyborylation of 4-chlorotoluene provides a trace amount of halogen-boron exchange product. No other products of oxyborylation were detected. The 3-fluorotoluene is defluorinated under the conditions of the reaction. Only a trace amount of the boron boronated material was observed in the ¹¹ B-NMR. 2-Methylthiophene is unreactive under the conditions of the reaction. In an independent experiment, using an equivimolar amount of 2-methylthiophene and m-xylene, it was confirmed that thiophene acts as a catalyst poison, and no oxyborylation was observed due to meta-xylene. A slight amount of oxyborylation of 2,6-dimethylpyridine was also observed by GC and GC-MS.

The reaction carried out using 3-methylanisole provides a product mixture resulting from a reduction-borylation sequence. Cobalt Complex 8 (10.2 mg, 0.02 mmol, 2 mol%) was placed in a 3 mL Wheaton® vial in a nitrogen-filled glove box. Then 0 THF (0.24 mL) and 3-methylanisole (126 [mu]L, 1.0 mmol) were added. Then, HBpin (290 μL, 2.0 mmol) was added. The vial is capped and removed from the glove box. The reaction mixture was then heated at 80 ° C for 18 h. Analysis by GC showed 11% alpha-Bpin-toluene, 25% alpha, alpha-diBpin-toluene, and 16% toluene.

The compositions and methods within the scope of the appended claims are not limited to the particular compositions and methods described herein. The specific compositions and methods described herein are intended to be illustrative of the scope of the invention. Any functionally equivalent composition and method are intended to fall within the scope of the claimed patent. Various modifications of the compositions and methods other than those shown and described herein are also intended to fall within the scope of the appended claims. Furthermore, although certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps are also intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components or components may be mentioned or not explicitly mentioned herein, however, other steps, elements, components or combinations of ingredients are also included, even if not stated.

As used herein, the term "comprising" and variations thereof are synonymous with the terms "including" and variations thereof, and are open, non-limiting terms. Although the terms "comprising" and "including" have been used herein to describe various specific examples, the term "substantially consists of" (consisting) The "consisting of" and "comprising" are intended to provide a more specific embodiment of the invention and are also disclosed. Except where specified, all numbers used in this specification and the scope of patent application to represent geometry, dimensions, etc., should be understood at the very least, and are not intended to limit the application of the scope of application to the scope of the patent application. The number of significant figures and the usual rounding method are explained.

All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains, unless otherwise defined. The publications listed herein, and the like, are hereby incorporated by reference.

Claims (43)

A method for preparing a monoboronated aromatic compound, comprising: an aromatic matrix and a catalytic cobalt complex and a boron oxynitride under conditions effective to form the boroborylated aromatic compound Contact with a reagent, wherein the catalytic cobalt complex is not one of the following: The method of claim 1, wherein the aromatic matrix is selected from the group consisting of a substituted or unsubstituted aryl compound, a substituted or unsubstituted six-membered heteroaromatic compound, A substituted or unsubstituted five-membered heteroaromatic compound, and combinations thereof. The method of claim 1 or 2, wherein the aromatic matrix is a substituted or unsubstituted aryl compound, and the substituted or unsubstituted aryl compound comprises a compound defined by formula I Wherein A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C ₆ alkyl group, C ₁ -C ₆ Haloalkyl, or a boronic acid or boronic acid derivative, each of R ¹ , R ² and R ³ being independently, hydrogen or C ₁ -C ₆ alkyl, and R ⁴ is independently present at each occurrence Is hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl; and wherein the oxyborylated aromatic compound comprises a compound defined by formula II Wherein A is as described above at each occurrence, and Y is a boronic acid or boronic acid derivative. The method of claim 3, wherein the oxyborylated aromatic compound comprises a compound defined by formula II, wherein Y is a boronic acid derivative selected from one of the group consisting of: The method of claim 1 or 2, wherein the aromatic matrix is a six-membered heteroaromatic compound, and the six-membered heteroaromatic compound comprises one defined by one of Formula IIIa, Formula IIIb, or Formula IIIc. Compound Wherein A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C ₆ alkyl group, C ₁ -C ₆ Haloalkyl, or a boronic acid or boronic acid derivative, each of R ¹ , R ² and R ³ being independently, hydrogen or C ₁ -C ₆ alkyl, and R ⁴ in each occurrence Independently, hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl; and wherein the oxyborylated aromatic compound comprises one of Formula IVa, Formula IVb, or Formula IVc Compound defined by Wherein A is as described above at each occurrence, and Y is a boronic acid or boronic acid derivative. The method of claim 5, wherein the oxyborylated aromatic compound comprises a compound defined by one of Formula IVa, Formula IVb, or Formula IVc, wherein Y is one selected from the group consisting of Boric acid derivatives: The method of claim 1 or 2, wherein the aromatic matrix is a five-membered heteroaromatic compound, and the five-membered heteroaromatic compound comprises a compound defined by one of Formula Va or Formula Vb. Wherein X is NH, O, or S; A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C _{a 6} alkyl group, a C ₁ -C ₆ haloalkyl group, or a boronic acid or a boronic acid derivative, each of which R ¹ , R ² and R ³ are independently, hydrogen or C ₁ -C ₆ alkyl And R ⁴ is, independently of each occurrence, hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl; and wherein the boroborylated aromatic compound comprises a formula VIa or a compound defined by one of Formula VIb Wherein A is as described above at each occurrence, and Y is a boronic acid or boronic acid derivative. The method of claim 7, wherein the oxyborylated aromatic compound comprises a compound defined by one of Formula VIa or Formula VIb, wherein Y is a boronic acid derivative selected from one of the group consisting of: The method of any one of claims 1-8, wherein the oxyborylation reagent comprises a B-B bond, a B-H bond, or a combination thereof. The method of any one of claims 1-9, wherein the oxyborylation reagent comprises one or more of the following: . The method of any one of claims 1 to 10, wherein the catalytic cobalt complex comprises a cobalt (I) complex. The method of any one of claims 1-11, wherein the catalytic cobalt complex comprises a cobalt-clamping complex comprising a double tooth ligand. The method of claim 12, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 2, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4 , R ⁶ is selected from those in one of the following: R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane group, R ⁹ at each occurrence is independently, C ₁ -C ₆ alkyl group, an aryl group, or -OR ^10, and R ¹⁰ at each occurrence is independently, C ₁ -C ₆ alkyl, or Aryl. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ⁷ is independently, on each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, Hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane group, and R ¹⁰ at each occurrence is independently, C ₁ -C ₆ alkyl or aryl. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, a halogen , -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0,1 , 2, 3, or 4, R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, and R ¹¹ and R ¹² are each independently selected from hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring, which is optionally 1 Substituted to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl, aryl a group, or a C ₁ -C ₆ haloalkyl group. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, a halogen , -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0,1 , 2, 3, or 4, B is -P(R ⁹ ) ₂ , -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , and R ⁷ is independently, in each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, and R ⁹ is independently, C ₁ -C ₆ alkane at each occurrence. a group, an aryl group, or -OR ¹⁰ , R ¹⁰ is independently a C ₁ -C ₆ alkyl or aryl group at each occurrence, and R ¹¹ and R ¹² are each independently selected from hydrogen, halogen, - OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and The attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C (=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl And the R ¹³ and R ¹⁴ are each independently selected from the group consisting of hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aromatic a group, or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents, the substitution The base is independently selected from the group consisting of halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group. . The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and B is -P(R ⁹ ) ₂ , -OR ¹⁰ Or -NR ¹⁰ R ¹⁰ , R ⁹ is independently at each occurrence, C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , R ¹⁰ is independently, on each occurrence, C ₁ -C ₆ alkyl or aryl, R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ An alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring which is optionally substituted by 1 to 4 substituents Substituted, the substituent is independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl, and R ¹³ and R ¹⁴ are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkane a aryl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted by from 1 to 4 substituents The substituent is independently selected from halogen, - OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, R ¹⁵ and R ¹⁶ systems are each independently Selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group Or R ¹⁵ and R ^{16 together} with their attached carbon atoms form a benzene ring which is optionally substituted by from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, R ⁷ is independently , hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is, independently of each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl. The method of any one of claims 1 to 11, wherein the catalytic cobalt complex comprises Py ₂ Co(CH ₂ SiMe ₃ ) ₂ , [(Cp ^* Co) ₂ -μ-(η ⁴ :η ⁴ - Toluene)], or a combination thereof. The method of any one of claims 1 to 23, wherein the aromatic matrix is contacted with the catalytic cobalt complex and the boron boronation reagent at a temperature greater than 25 ° C to 85 ° C. Method for preparing a compound defined by formula VII Wherein X is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and Y is a boronic acid or a boronic acid derivative, the method comprising: providing an aromatic matrix comprising a a substituted aryl group or a methyl substituted heteroaryl group; and the effective formation of the compound defined by the formula VII, the aromatic matrix and a catalytic cobalt complex and monoboronylation Reagent contact. The method of claim 25, wherein X is a substituted or unsubstituted phenyl group or a substituted or unsubstituted pyridyl group. The method of claim 25 or 26, wherein the aromatic matrix is a substituted or unsubstituted aryl compound, and the substituted or unsubstituted aryl compound comprises a compound defined by formula VIII Wherein A is independently at each occurrence, hydrogen, halogen, -OR ¹ , -NR ² R ³ , -C(=O)R ⁴ , nitrile group, C ₁ -C ₆ alkyl group, C ₁ -C ₆ Haloalkyl, or a boronic acid or boronic acid derivative, each of R ¹ , R ² and R ³ being independently, hydrogen or C ₁ -C ₆ alkyl, and R ⁴ in each occurrence Independently, hydrogen, -OR ¹ , -NR ² R ³ , or C ₁ -C ₆ alkyl; and wherein the oxyborylated aromatic compound comprises a compound defined by formula IX Wherein A is as described above at each occurrence, and Y is a boronic acid or boronic acid derivative. The method of claim 27, wherein the oxyborylated aromatic compound comprises a compound defined by formula II, wherein Y is a boronic acid derivative selected from one of the group consisting of: The method of any one of claims 25-28, wherein the oxyborylation reagent comprises a B-B bond, a B-H bond, or a combination thereof. The method of any one of claims 25-29, wherein the oxyborylation reagent comprises one or more of the following: The method of any one of claims 25-30, wherein the catalytic cobalt complex comprises a cobalt (II) complex. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein at each occurrence Z is independently, a halide, C ₁ -C ₆ alkyl group, or aryl group, n is is 2, R ⁵ at each occurrence is independently, halogen, -OR ^7, -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, The R ⁶ is selected from one of the following: R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane a group, R ⁹ is, independently of each occurrence, independently C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, in each occurrence, C ₁ -C ₆ alkyl or Aryl. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ⁷ is independently, on each occurrence, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, Hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, m is 0, 1, or 3, R ⁷ for each occurrence is independently, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently , C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , and R ¹⁰ is independently, on each occurrence, a C ₁ -C ₆ alkyl or aryl group. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and E is -CH ₂ -, -C(R ¹⁰ ) ₂ -, -NR ⁷ -, -S-, or -O-, R ⁵ is independently at each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, or 3, and L is -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ^{7 is} Each occurrence is independently hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkane group, and R ¹⁰ at each occurrence is independently, C ₁ -C ₆ alkyl or aryl. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, R ⁷ is independently at each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ is independently at each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ or C ₁ -C ₆ alkyl, and R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring, which is selectively 1 Substituted to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group , or a C ₁ -C ₆ haloalkyl group. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n being 0, 1, 2, or 3, and R ⁵ is independently, in each occurrence, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, m is 0, 1, 2, 3, or 4, B is -P(R ⁹ ) ₂ , -OR ¹⁰ or -NR ¹⁰ R ¹⁰ , R ⁷ is independently, on each occurrence, hydrogen or C ₁ -C ₆ alkyl, R ⁸ at each occurrence is independently hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl, R ⁹ is independently at each occurrence, C ₁ -C ₆ alkyl , aryl, or -OR ¹⁰ , R ¹⁰ is independently, in each occurrence, a C ₁ -C ₆ alkyl or aryl group, and R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , a nitrile group, a C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and The attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C( =O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group And R ¹³ and R ¹⁴ are each independently selected from the group consisting of hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group Or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted with from 1 to 4 substituents, the substituent It is independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group. The method of any one of claims 25-31, wherein the catalytic cobalt complex comprises a complex defined by the formula Wherein Z is independently, at each occurrence, a halide, a C ₁ -C ₆ alkyl group, or an aryl group, n is 0, 1, 2, or 3, and B is -P(R ⁹ ) ₂ , -OR ¹⁰ Or -NR ¹⁰ R ¹⁰ , R ⁹ is independently at each occurrence, C ₁ -C ₆ alkyl, aryl, or -OR ¹⁰ , R ¹⁰ is independently, on each occurrence, C ₁ -C ₆ alkyl, or aryl, R ¹¹ and R ¹² are each independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C _{a 6} alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹¹ and R ¹² and their attached carbon atoms together form a benzene ring which is optionally substituted by 1 to 4 substituents Substituted, the substituent is independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ - C ₆ haloalkyl, and R ¹³ and R ¹⁴ are each independently selected from the group consisting of hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ An alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl group, or R ¹³ and R ¹⁴ and their attached carbon atoms together form a benzene ring which is optionally substituted by 1 to 4 substituents Substituted, the substituent is independently selected from halogen ^{-OR 7, -NR 7 R 7,} -C (= O) R 8, nitrile, C ₁ -C ₆ alkyl group, an aryl group, or a C ₁ -C ₆ haloalkyl, R ¹⁵ and R ¹⁶ are each system Independently selected from, hydrogen, halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkane a group, or R ¹⁵ and R ^{16 together} with their attached carbon atoms, form a benzene ring which is optionally substituted with from 1 to 4 substituents independently selected from halogen, -OR ⁷ , -NR ⁷ R ⁷ , -C(=O)R ⁸ , nitrile group, C ₁ -C ₆ alkyl group, aryl group, or C ₁ -C ₆ haloalkyl group, R ⁷ is independently present at each occurrence That is, hydrogen or C ₁ -C ₆ alkyl, and R ⁸ is independently, on each occurrence, hydrogen, -OR ⁷ , -NR ⁷ R ⁷ , or C ₁ -C ₆ alkyl. The method of any one of claims 25-41, wherein the catalytic cobalt complex comprises Py ₂ Co(CH ₂ SiMe ₃ ) ₂ , [(Cp ^* Co) ₂ -μ-(η ⁴ :η ⁴ - Toluene)], N-heterocyclic carbene-ligated cobalt complex, or combinations thereof. The method of any one of claims 25-42, wherein the aromatic matrix is The catalytic cobalt complex and the boron boronation reagent are contacted at a temperature greater than 25 ° C to 80 ° C.